JP5226953B2 - Detergent particles - Google Patents

Description

  The present invention relates to detergent particles and detergent compositions.

The detergent composition in powder form may cause caking that becomes a solidified state when the particles of the detergent composition are combined with each other during long-term storage. It is done. Surfactants are generally liquid at room temperature, and therefore, by exuding from a powdered detergent composition, the adhesion between the particles of the detergent composition is increased, the flow characteristics of the particles are reduced, and caking There is a problem that causes The caking that occurs in this manner not only significantly impairs the appearance, but also makes the usability of the detergent significantly worse, such as being unable to accurately measure.
In order to solve such a problem, a granular nonionic detergent composition containing a clay mineral having an oil absorption of less than 80 ml / 100 g and an oil-absorbing carrier of 80 ml / 100 g or more has been proposed (for example, Patent Document 1). However, since the oil-absorbing carrier does not contribute to the cleaning performance, it is not sufficient from the viewpoints of restrictions on formulation and relatively expensive, resulting in an increase in manufacturing cost.
Patent Document 2 proposes a method of suppressing caking by obtaining free fluidity by mixing a granular detergent composition and a liquid binder substance and then coating with zeolite X as a surface modifier. However, the adherence of zeolite X is not sufficient, and zeolite X peels off due to the stress applied to the detergent particles during the transportation of the manufacturing process, etc., but the caking suppressing effect exhibited when using the detergent particles is sufficient. There wasn't.
Further, a method for suppressing caking by treating the surface of the base particles with a liquid in which fine powders of clay minerals are dispersed in a binder and improving the adhesion of the modifier has been proposed (for example, Patent Document 3). However, it is sufficient in terms of requiring a step of finely pulverizing the fine powder to be dispersed in the binder to 0.1 to 5 μm, a facility for preparing the dispersion, and suppressing the occurrence of surfactant stains. There wasn't. Under such circumstances, there has been a demand for a detergent particle and a detergent composition which are more excellent in the anti-smudge property of the surfactant (excellent in caking resistance).

Japanese Patent No. 3043976 Japanese Patent No. 2954805 JP 2004-143394 A

  It is an object of the present invention to provide detergent particles excellent in storage stability such as caking resistance and surfactant stain suppression, and a detergent composition containing the detergent particles.

The present inventors have found that the above problem can be solved by detergent particles containing base detergent particles, a specific layered clay mineral, and a surface modifier.
That is, the present invention provides the following detergent particles.
The base detergent particles comprising 1 to 25 parts by weight of a layered clay mineral (b) having an average particle diameter of 1 to 80 μm and a surface modifier (c) with respect to 100 parts by weight of the base detergent particles (a). Detergent particles obtained by forming an intermediate layer containing the layered clay mineral (b) on the surface of (a) and adding the surface modifier (c) on the intermediate layer.

  The detergent particles of the present invention are excellent in storage stability such as caking resistance and suppression of surfactant stains.

The detergent particles of the present invention contain 1 to 25 parts by mass of a layered clay mineral (b) having an average particle diameter of 1 to 80 μm and a surface modifier (c) with respect to 100 parts by mass of the base detergent particles (a). An intermediate layer containing the layered clay mineral (b) is formed on the surface of the base detergent particles (a), and the surface modifier (c) is added to the intermediate layer. is there.
Hereinafter, the detergent particles of the present invention will be described in detail.

[Base detergent particles (a): spray-dried particles (e)]
The base detergent particles (a) refer to particles before the formation of an intermediate layer containing a lamellar clay mineral (b) described later and the surface modification by the surface modifier (c). Such base detergent particles (a) preferably contain base particles (a ′), a surfactant composition (d), and other components.

  The base particles (a ′) can be prepared by, for example, drying a slurry containing a substrate having a metal ion sequestering ability or an alkali ability into a granular form, and among others, the slurry is obtained by spray drying. The spray-dried particles (e) are preferred from the viewpoint of obtaining desired physical property values.

The slurry used for the preparation of the spray-dried particles (e) preferably contains a water-insoluble mineral, a water-soluble polymer, and water-soluble salts.
The water-insoluble inorganic substance is preferably an inorganic substance capable of dissolving less than 10 g (preferably less than 5 g, more preferably less than 1 g) in 100 g of water at 20 ° C., specifically, an aluminosilicate having a sequestering ability; Examples thereof include clay compounds such as silicon dioxide, hydrated silicic acid compound and perlite.
As the water-soluble polymer, those capable of dissolving 1 g or more (preferably 5 g or more, more preferably 10 g or more) in 100 g of water at 20 ° C. are preferable. Specific examples include carboxylic acid polymers, carboxymethylcellulose, soluble starch, saccharides, etc., and have a weight average molecular weight of several thousand in terms of sequestering ability, dispersibility of solid dirt / particle dirt and ability to prevent recontamination. 100,000 to carboxylic acid polymers are preferred. Particularly preferred are acrylates and salts of acrylic acid-maleic acid copolymers.
As the water-soluble salts, the same water-soluble salts as the above water-soluble polymers are preferable. Specifically, alkali metal salt, ammonium salt, or amine each having an alkali ability carbonate ion, bicarbonate ion, silicate ion, sulfate ion, sulfite ion, hydrogen sulfate ion, hydrochloric acid ion, phosphate ion, or the like Examples thereof include water-soluble inorganic salts typified by salts, and low-molecular-weight water-soluble organic salts such as citric acid and fumarate having a sequestering ability.

The contents of the water-insoluble inorganic substance, the water-soluble polymer, and the water-soluble salt contained in the slurry are preferably 20 to 90% by mass, 2 to 30% by mass, and 5 to 78% by mass, respectively, based on the solid content. The range of 30-75 mass%, 3-20 mass%, 10-67 mass% is more preferable, and it is still more preferable that they are 40-70 mass%, 5-20 mass%, and 20-55 mass%. By adjusting the drying method and drying conditions within the above composition range, the average particle diameter, bulk density, supporting ability, and particle strength can be controlled.
In addition to the water-insoluble inorganic substance, water-soluble polymer, and water-soluble salt, the slurry contains particles, salts, surfactants, and dyes that are suitable for the cleaning composition obtained by the present invention as other components. An auxiliary component such as For example, surfactants and fluorescent dyes can be used. The blending amount of the other components is preferably 10% by mass or less in the slurry.

The base particles (a ′) preferably have the following structure (1) and / or (2).
Structure (1): When detergent particles are dissolved in water, the particle size of the detergent particles is preferably 1/10 or more, more preferably 1/5 or more, still more preferably 1/4 or more, and particularly preferably 1/3 or more. It is preferable to have pores capable of releasing bubbles having a diameter of.
Structure (2): a water-insoluble inorganic substance, a water-soluble polymer, and a water-soluble salt, and an uneven distribution in which more water-soluble polymers and / or water-soluble salts (hereinafter referred to as water-soluble polymers) exist near the surface than inside It is preferable to have properties.
When the base particles (a ′) have the structure (1), when a small amount of water enters the particles in the process of dissolving the detergent particles in water, bubbles of a predetermined size are released from the inside of the particles. Next, when a large amount of water intrudes into the particle, the particle itself collapses (self-disintegration), so that the detergent particles dissolve not only from the vicinity of the surface but also dissolve and disintegrate from the inside of the particles, so that the detergent particles dissolve at high speed. Have sex.

  This bubble emission phenomenon can be confirmed with a digital microscope or an optical microscope, and the bubble diameter (equivalent circle diameter) can be measured. The pore diameter of the base particles (a ′) is preferably 1/10 to 4/5, more preferably 1/5 to 4/5 of the particle diameter. The pore diameter can be measured as follows. Cut the base particle (a ′) with a scalpel or the like so as not to break the base particle (a ′), and observe the cut surface with a scanning electron microscope. The equivalent circle diameter (γ μm) of the cut surface of the cut particle and the inside of the particle If the presence of pores is confirmed in step 1, the equivalent circle diameter (δ μm) of the pores is measured. When a plurality of pores are confirmed, the equivalent circle diameter of the largest pore is δ μm. Then, the ratio of pore diameter to particle diameter (δ / γ) is obtained.

  In addition, since the base particles (a ′) have the structure (2), the water-soluble components in the vicinity of the surface dissolve faster in water, so that the dissolution behavior of the detergent particles from the particle surface is promoted. By showing, high-speed solubility can be expressed. In addition, the most preferable mode for expressing the high-speed solubility is that the base particles (a ′) have both the structures (1) and (2).

The uneven distribution of the water-soluble polymer can be confirmed by the following method. First, base particles (a ′) to be measured and base particles (a ′) pulverized products in which the base particles (a ′) are sufficiently pulverized with an agate mortar or the like to prepare a uniform state are prepared. Then, under the condition that information from the surface of the pulverized product of the base particle (a ′) and the base particle (a ′) to about 10 μm is obtained, both of them are subjected to Fourier transform infrared spectroscopy (FT-IR) and photoacoustic spectroscopy, respectively. (PAS) is used in combination (hereinafter referred to as “FT-IR / PAS”). When the amount of the former water-soluble polymer or the like is larger than that of the latter, the base particle (a ′) to be measured has a structure in which more water-soluble polymer or the like is present near the surface than inside. As measurement conditions for obtaining information from the surface of the pulverized base particles (a ′) and the base particles (a ′) to about 10 μm, for example, resolution 8 cm ⁻¹ , scan speed 0.63 cm / s, total 128 times, The condition is mentioned. Examples of the apparatus to be used include an FTS-60A / 896 type infrared spectrophotometer manufactured by Bio-Rad Laboratories as an infrared spectrophotometer, and a 300 type photoacoustic detector manufactured by MTEC as a PAS cell. In addition, FT-IR / PAS is APPLIED SPECTROCOPY VOL. 47 1311-1316 (1993).

[Base detergent particles (a): physical properties of base particles (a ′)]
The average particle size of the primary particles of the base particles (a ′) thus obtained is preferably 150 to 500 μm, more preferably 180 to 350 μm, from the viewpoint of obtaining detergent particles excellent in solubility and flow characteristics. The bulk density is preferably 400 g / L or more, more preferably 450 g / L or more, from the viewpoint that detergent particles having excellent solubility can be obtained and compactness can be achieved. A method for measuring the average particle size and bulk density of the base particles (a ′) will be described later.

The base particles (a ′) preferably have a higher ability to carry a liquid component (supporting ability). The carrying capacity is preferably 20 mL / 100 g or more, and more preferably 40 mL / 100 g or more. If the carrying ability is within the above range, aggregation of the base particles (a ′) is suppressed, and aggregation of the particles in the detergent particles can be suppressed.
The primary particles of the base particles (a ′) are preferably hard particles. Specifically, the particle strength is preferably 100 kg / cm ² or more, more preferably 200 kg / cm ² or more. If the particle strength is within the above range, the base detergent particles can be sufficiently prevented from collapsing during the production process.

The supporting ability of the base particles (a ′) is measured as follows. 100 g of a sample was placed in a cylindrical mixing tank having an inner diameter of 5 cm and a height of 15 cm and equipped with a stirring blade inside. While stirring the stirring blade at 350 rpm, polyoxyethylene alkyl ether (product name, manufactured by Kao Corporation) at 25 ° C. : Emulgen 108KM) is introduced into the tank at a rate of 10 mL / min. The loading amount of polyoxyethylene alkyl ether when the power required for stirring becomes the highest is defined as the supporting ability.
Moreover, the measurement of the particle | grain intensity | strength of base particle | grains (a ') is performed as follows. 20 g of sample is put in a cylindrical container having an inner diameter of 3 cm and a height of 8 cm, and tapped 30 times (Tsutsui Rikenki Co., Ltd., TVP1 type tapping type densely packed bulk density measuring device, tapping condition; period 36 times / min, 60 mm Free fall from the height. The sample height immediately after the end of the tapping operation is measured and set as the initial sample height. Thereafter, the entire upper end surface of the sample held in the container by a pressure tester is pressurized at a speed of 10 mm / min, and a load-displacement curve is measured. The initial sample height is multiplied by the slope of the straight line when the displacement rate in the curve is 5% or less, and the value obtained by dividing the obtained value by the pressurized area is defined as the particle strength.

[Base detergent particles (a): surfactant composition (d)]
The surfactant composition (d) preferably used for forming the base detergent particles comprises at least one selected from an anionic surfactant, a nonionic surfactant, a zwitterionic surfactant, and a cationic surfactant. It is obtained by blending as necessary. The surfactant composition (d) is preferably in a liquid state when the base detergent particles (a) are produced.
Anionic surfactants include higher alcohol sulfates, higher alcohol ethoxylate sulfates, alkylbenzene sulfonates, paraffin sulfonates, α-olefin sulfonates, α-sulfo fatty acid salts or alkyls thereof. Examples thereof include an anionic surfactant having a sulfuric acid group or a sulfonic acid group such as an ester salt or a fatty acid salt. In particular, a linear alkylbenzene sulfonate having 10 to 18 carbon atoms, more preferably 12 to 14 carbon atoms, and a sulfate ester salt of a higher alcohol having 10 to 16 carbon atoms, and more preferably 12 to 14 carbon atoms are preferable.
Examples of the nonionic surfactant include ethylene oxide (hereinafter referred to as “EO”) adducts of higher alcohols, or EO / propylene oxide (hereinafter referred to as “PO”) adducts, fatty acid alkanolamides, alkyl polyglycosides, and the like. In particular, EO 1-10 mol adducts of alcohols having 10 to 16 carbon atoms are effective in removing sebum stains, hard water resistance, biodegradability and compatibility with linear alkylbenzene sulfonates and sulfates of higher alcohols. This is preferable.
Examples of amphoteric surfactants include alkyldimethylaminoacetic acid betaines and fatty acid aminopropyl betaines, and examples of cationic surfactants include mono (or di) long chain alkyl quaternary ammonium salts.

Surfactant composition (d) comprises 0 to 300 parts by mass of an anionic surfactant (b) having a sulfate group or a sulfonate group with respect to 100 parts by mass of nonionic surfactant (a) and the nonionic surfactant. A surfactant composition comprising 1 to 100 parts by mass of a surfactant fixing agent (C) is preferred. In the composition, (b) is more preferably 20 to 200 parts by mass, particularly preferably 30 to 180 parts by mass. Moreover, (ha) has more preferable 5-50 mass parts, and 5-30 mass parts is especially preferable. When such a surfactant composition (d) is used, the solubility and flow properties of the detergent particles are improved, the collapse of the spray-dried particles during mixing, and the surfactant stains during storage (at room temperature). Is particularly preferable. The addition of an anionic surfactant having a sulfuric acid group or a sulfonic acid group is further advantageous for improving the flow characteristics of the detergent particles and suppressing the occurrence of the surfactant stain during storage (at room temperature).
The nonionic surfactant immobilizing agent (c) suppresses the fluidity of the liquid nonionic surfactant at room temperature and significantly increases the hardness in a state where the surfactant composition has lost its fluidity. It is a possible base. Examples of the immobilizing agent include fatty acid salts, polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, and pluronic type nonionic surfactants.

  The content of the surfactant composition (d) in the base detergent particles (a) is usually about 0 to 50% by mass, preferably 10 to 50% by mass from the viewpoint of exerting detergency, and the lower limit is 15 More preferably, it is more preferably 20% by mass or more, more preferably 20% by mass or more, and more preferably 45% by mass or less, even more preferably 40% by mass. If surfactant (d) exists in the said range, the base detergent particle | grains excellent in solubility will be obtained.

[Base detergent particles (a): production method of base detergent particles (a)]
The method for producing the base detergent particles (a) is not particularly limited as long as particles having the above physical properties can be obtained, but as a typical example, spray drying in which a slurry containing each of the above components is spray dried. And a method of increasing the bulk density of particles having a low bulk density obtained by spray-drying the slurry by a stirring granulation method, a tumbling granulation method, a method of granulating by a mixing / extrusion method, etc. it can. In the case of granulation by the mixing / extrusion method, pulverization after extrusion is preferable for improving the fluidity and appearance of the particles. Among such production methods, the liquid surfactant composition (d) is supported on the spray-dried particles (e) obtained by spray-drying the slurry which does not substantially contain the surfactant composition (d). The method of obtaining the base detergent particles (a) is particularly preferred from the viewpoint of the solubility and flow characteristics of the obtained particles.

A solid anionic surfactant neutralized product obtained by a dry neutralization method in which a neutralization reaction is performed with an acid precursor of an anionic surfactant and solid alkali particles is also suitable as the base detergent particle (a). is there. When the dry neutralization method is used, there is an advantage that the equipment becomes compact because the spray drying process is not necessary. The neutralization method at the time of dry neutralization is not particularly limited, and neutralization may be performed by kneading / kneading, followed by crushing granulation, or neutralization reaction while applying shearing force in a stirring granulator May be performed.
The base detergent particles (a) may be obtained by dry-mixing separate particles obtained by a method such as spray drying or dry neutralization, or other particles such as alkali particles may be dry-mixed. For example, heavy sodium carbonate (dense ash) particles may be mixed with particles containing a surfactant produced by a spray drying method or the like to achieve a target composition. That is, the production method is not limited for each particle used for mixing.

[Layered clay mineral (b)]
The layered clay mineral (b) according to the present invention forms an intermediate layer formed on the surface of the base detergent particles (a). The thickness of the intermediate layer is naturally determined from the size of the base detergent particles (a), the average particle diameter of the layered clay mineral (b) forming the intermediate layer, the amount added, etc., but usually 1 to 80 μm is preferable. 1 and 2 are SEM photographs of cross sections of the detergent particles obtained in the examples of the present invention, in which an intermediate layer of layered clay mineral (b) is formed on the surface of the base detergent particles (a). Can be confirmed.

  Layered clay minerals (b) include talc, pyrophyllite, smectite (saponite, hectorite, saconite, stevensite, montmorillonite, beidellite, nontronite, etc.), vermiculite, mica (phlogopite, biotite, chinwald mica, Muscovite, paragonite, ceradonite, sea chlorite, etc.), chlorite (clinochlore, chamosite, nimite, penantite, sudowite, dombasite, etc.), brittle mica (clinintite, margarite, etc.), sulite, serpentine mineral (anti Examples include golite, lizardite, chrysotile, amicite, clonstedite, burcherin, greenerite, garnierite, and kaolin minerals (kaolinite, dickite, nacrite, halloysite, etc.). Of these, talc, smectite, swellable mica, vermiculite, chrysotile, kaolin mineral, and the like are preferable, smectite is more preferable, and montmorillonite is further preferable in terms of flexibility. These may be used alone or in appropriate combination of two or more.

In addition, the following general formula (I):

It is preferable that a clay mineral represented by Here, a, b and x are 0 <a ≦ 6, 0 <b ≦ 4, x = 12-2a-3b, and Me is Na, K, Li, Ca _1/2 , Mg _1/2 and It is at least one ion selected from NH ₄ .

  Such a layered clay mineral (b) is excellent in the ability to absorb liquid components between layers. Therefore, it becomes possible to suppress the stain of the liquid surfactant composition (d) described above. In addition, when the liquid component is contained, the adhesiveness is increased, and the surface modifier (c) described later can be maintained on the particle surface to prevent peeling, so that the coverage of the surface modifier (c) is increased. It can be preferably used.

Examples of the layered clay mineral represented by the general formula (I) include “Round rosyl DGA212”, “Round rosyl PR414”, “Round rosyl DG214”, “Round rosyl DGA powder”, “EXM0242”, “Hulasoft” manufactured by Sud Kemi. −1 powder ”,“ Detasoft GIS ”,“ Detasoft GIB ”,“ Detasoft GISW ”manufactured by Raviossa, Pure Bentonite, Standard Bentonite, Premium Bentonite manufactured by CSM, and the like. Among the above-mentioned examples of layered clay minerals, there are granulated granule types added with a binder component, but the binder component may be added as long as the effects of the present invention are not impaired. Good.
When using the lamellar clay minerals listed above as the lamellar clay mineral (b) according to the present invention, in order to efficiently disperse as an intermediate layer on the surface of the base detergent particles, it should be crushed in advance until a suitable particle size is obtained. Is preferred. Examples of the crusher that can be used for crushing include impact crushers such as hammer crushers, impact crushers such as atomizers and pin mills, and shear crushers such as flash mills. These may be a single-stage operation or a multi-stage operation of the same or different pulverizers.

From the viewpoints of storage stability and solubility, the layered clay mineral represented by the general formula (I) is composed of alkali metal ions (total of Na ions, K ions, Li ions) and alkaline earth metal ions (Ca ions). , Mg ion) (Na + K + Li) / (Ca + Mg) is preferably 1.0 or more, more preferably 1.5 or more, and even more preferably 2.0 or more.
In order to obtain a layered clay mineral with a high ratio of alkali metal ions, if it is a natural product, it is sufficient to select the production area, and when producing a granulated granule, it is also possible to adjust by adding an alkali metal salt. it can. Moreover, if it is a synthetic | combination product, it can adjust arbitrarily by a well-known method.
Further, as a method for producing a layered clay mineral having a high alkali metal ion ratio, the following production method is useful. A method that includes a step of drying after adding an alkali metal salt such as powdered sodium carbonate to a raw clay ore containing 20% or more of water and mixing it, or making a powdered clay mineral with a granulator This is a production method including a step of adding a powder or an aqueous solution of an alkali metal salt such as sodium carbonate when granulating.

  The ratio of alkali metal ions to alkaline earth metal ions in the layered clay mineral (b) is measured by the following method. The layered clay mineral (b) is pulverized in a mortar, and 0.1 g of a sample that has passed through a sieve having an opening of 125 μm is decomposed with sulfuric acid-hydrogen peroxide using a microwave wet ashing device (automatic), and then made up to 50 mL in a volumetric flask. After measuring up, the amount of Na, K, Li, Ca, and Mg is measured and measured with an ICP emission spectrometer and calculated.

The amount of the layered clay mineral (b) added is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more with respect to 100 parts by mass of the base detergent particles (a) in order to obtain the effect of the present invention sufficiently. More preferably, it is 2 parts by mass or more. Moreover, 25 mass parts or less are preferable, 23 mass parts or less are more preferable, and 20 mass parts or less are still more preferable. The average particle size of the layered clay mineral (b) is preferably 80 μm or less, more preferably 60 μm or less, further preferably 40 μm or less, and particularly preferably 20 μm or less. Moreover, 1 micrometer or more is preferable, 3 micrometers or more are more preferable, 5 micrometers or more are further more preferable, and 7 micrometers or more are especially preferable. If the addition amount and the average particle diameter are within this range, a sufficient effect of improving the caking resistance can be expected after avoiding a decrease in solubility. In addition, since the layered clay mineral (b) contains impurities such as quartz, cristobalite, calcite, feldspar, etc., especially in the case of natural, the content of the layered clay mineral (b) includes those impurities. It is.
Here, the average particle size of the layered clay mineral (b) can be measured using, for example, a laser diffraction / scattering particle size distribution measuring apparatus having a dry measurement unit. Specifically, measurement can be performed by optionally connecting a dry measurement unit G0310630 to Partica LA-950 (manufactured by Horiba, Ltd.) using the Mie scattering method. The compressed air setting for dispersing the powder is measured under normal conditions, and the median diameter obtained is taken as the average particle diameter of the layered clay mineral (b).

[Surface modifier (c)]
The surface modifier (c) is added onto the intermediate layer containing the layered clay mineral (b) formed on the surface of the base detergent particles (a) to modify the surface of the detergent particles. The surface modifier (c) may be present on the outermost surface of the detergent particles (a) depending on the average particle diameter, the amount used, etc., or is taken into the intermediate layer formed by the layered clay mineral (b). Although it may exist in a state, it does not affect the effect of the present invention depending on the mode.
Examples of the surface modifier (c) include fine powders, liquids, and fatty acids. Among these, fine powders are preferable. The average particle size of the primary particles of the fine powder of the surface modifier (c) is preferably 10 μm or less, and more preferably 0.1 to 10 μm. If the average particle size is within this range, the coverage of the surface modifier (c) on the intermediate layer formed on the surface of the base detergent particles (a) is improved, so that the flowability and caking resistance of the detergent particles are improved. It is suitable from the viewpoint of improving the above. Here, the average particle diameter of the fine powder is measured by a method using Mie scattering, for example, LA-920 (manufactured by Horiba, Ltd.). Moreover, it is preferable from a washing | cleaning surface that this fine powder has a high ion exchange ability and a high alkali ability.

Examples of the fine powder preferably used as the surface modifier (c) include crystalline or amorphous aluminosilicates. Other examples include fine powders such as silicate compounds such as sodium sulfate, calcium silicate, silicon dioxide, amorphous silica derivatives, and crystalline silicate compounds. Moreover, the metal soap whose primary particle is 0.1-10 micrometers, powdery surfactant (for example, alkyl sulfate etc.), water-soluble organic salt, etc. are mentioned. When a crystalline silicate compound is used, it is preferably used by mixing with a fine powder other than the crystalline silicate compound for the purpose of preventing deterioration due to moisture absorption or aggregation of the crystalline silicate due to carbon dioxide gas.
The amount of the surface modifier used is preferably 0.5 to 35% by mass, more preferably 1 to 30% by mass, and particularly preferably 2 to 25% by mass in the detergent particles. When the amount of the fine powder used is within this range, the fluidity is improved, giving the consumer a good feeling of use.

[Other components: Binder component]
In the present invention, it is preferable to add a binder component in order to further improve the adhesion between the layered clay mineral (b) forming the intermediate layer and the surface modifier (c).
Examples of the binder component include one or more selected from the surfactant composition (d) described above, polyethylene glycol, (meth) acrylic acid polymers, cellulose derivatives, and aqueous solutions thereof. Polyethylene glycol having an average molecular weight of 4000 or more and 20000 or less is preferable from the viewpoint of solidification at a temperature at which a detergent is usually used (˜40 ° C.) and solubility after surface treatment. Examples of the cellulose derivative include carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose and the like.

Moreover, as a binder component, the acid precursor of the anionic surfactant shown below can also be mentioned preferably. The acid precursor of the anionic surfactant is a substance that causes a neutralization reaction with the alkaline agent contained in the spray-dried particles, such as alkylbenzene sulfonic acid, alkyl or alkenyl ether sulfuric acid, alkyl or alkenyl sulfuric acid, α-olefin. Examples include sulfonic acid, α-sulfonated fatty acid, alkyl or alkenyl ether carboxylic acid, and fatty acid. Among them, those having high water resistance are preferable. Particularly preferable acid precursors include fatty acids, hydroxy fatty acids, alkyl phosphoric acids and the like. In particular, one or more selected from fatty acids having 10 to 22 carbon atoms or hydroxy fatty acids are preferable from the viewpoint of solubility. Particularly preferred is at least one selected from saturated fatty acids having 12 to 20 carbon atoms in terms of detergent particle strength.
As addition amount of a binder component, 0-8 mass parts is preferable with respect to 100 mass parts of base detergent particles, 0.5-6 mass parts is more preferable, and 1-4 mass parts is further more preferable.

[Other ingredients: Alkaline buffer]
In the present invention, as other components, spray-dried particles (e) and powders and / or granules having alkali buffering ability (hereinafter referred to as alkali buffering agent) are mixed in advance to obtain a surfactant composition (d ). Examples of the alkali buffer include alkali metal silicates and carbonates.
As the alkali metal carbonate, sodium carbonate is preferable, and either dense ash (heavy ash) or light ash (light ash) may be used. It is also possible to adjust the bulk density by changing the ratio of dense ash and light ash.

  In addition, the alkali metal silicate is preferably one having ion exchange ability and dissolved in water to exhibit alkalinity. The ion exchange capacity can be measured, for example, by a method for measuring the Ca ion exchange capacity. The value is not particularly limited, but is preferably 10 to 250 mg / g, and particularly preferably 50 to 250 mg / g. More preferably, it is 120-250 mg / g, and the thing of this area | region is effective at the point which can be mix | blended with a compact detergent, when using as a Ca ion exchanger for detergents, and is effective at a small quantity.

  As an alkali metal silicate having such ion exchange capacity, the following general formula (II):

A composition represented by the formula is preferred. Here, M represents Na and / or K, Me represents Ca and / or Mg, y / x = 0.5 to 4.0, z / x = 0 to 1.0, Mg / in MeO Ca (molar ratio) = 0 to 10. Examples of the alkali metal silicate having such a composition include sodium metasilicate, potassium metasilicate, powder No. 1 sodium silicate, powder No. 2 sodium silicate and the like. In addition, a crystalline alkali metal silicate described in JP-B-1-41116 is exemplified as an alkali metal silicate having a particularly high ion exchange capacity.
As a more preferable alkali metal silicate that expresses higher ion exchange capacity, y / x = 1.0 to 2.1, z / x = 0.001 to 1.0 in the above composition formula (II). Alkali metal silicates. As the alkali metal silicate having such a composition, a synthetic inorganic builder described in Japanese Patent No. 2525318 is suitable.

Moreover, the storage stability can be further improved by using an alkali metal silicate containing potassium. As a composition of such an alkali metal silicate containing potassium, in the above formula (II), y / x = 1.4 to 2.1, z / x = 0.001 to 1.0, A composition represented by K / Na (molar ratio) in M ₂ O = 0.09 to 1.11. As such an alkali metal silicate, a crystalline alkali metal silicate described in Japanese Patent No. 2525342 is particularly preferable.

Among the crystalline alkali metal silicates, the most preferable is the crystalline layered sodium disilicate Na _{2 where} x = 1, y = 2, z = 0 and M = Na in the general formula (II). Si ₂ O ₅ .wH ₂ O. Crystalline layered sodium disilicate is composed of polymorphic phases with varying proportions of α, β, δ and ε. In commercial products, an amorphous fraction may also be present, so the value of y in commercial products may be an odd number. Preferably, y is 1.9 or more and 2.2 or less. Preferred crystalline layered sodium disilicate is α-sodium disilicate in a proportion of 0-40% by mass, β-sodium disilicate in a proportion of 0-40% by mass, δ-sodium disilicate in a proportion of 40-100% by mass. , And consists of an amorphous fraction in a proportion of 0 to 40% by mass. Particularly preferred crystalline layered sodium disilicate is α-sodium disilicate in a proportion of 7 to 21% by mass, β-sodium disilicate in a proportion of 0 to 12% by mass, δ-disilicate in a proportion of 65 to 95% by mass. Sodium, consisting of an amorphous fraction with a proportion of 0-20% by weight. Most preferred is crystalline layered sodium disilicate containing δ-sodium disilicate in a proportion of 80 to 100% by mass. As the crystalline alkali metal silicate, those exemplified above may be used alone, or several kinds may be mixed and used as a mixture.

  10-50 mass parts is preferable with respect to 100 mass parts of spray-dried particle (e), and, as for the compounding quantity of the alkaline buffer mixed beforehand with spray-dried particle (e), 20-40 mass parts is more preferable. If it is in this range, sufficient cleaning performance and oil absorption ability can be expected.

[Method for producing detergent particles]
The detergent particles of the present invention are not limited by the production method, but are limited by the final particle morphology and particle composition. Therefore, a preferable production method for realizing the present invention is disclosed below, but the present invention is not limited to the following production method.
The detergent particles for realizing the present invention include a step [1] of preparing base detergent particles (a), and a step of forming an intermediate layer by adding layered clay mineral (b) to the base detergent particles (a) [2]. The particles having the intermediate layer obtained in the step [2] can be produced by undergoing a step [3] for surface modification with the surface modifier (c).

[Step [1]]
Step [1] is a step of preparing base detergent particles (a), a step of preparing slurry [A], a step of spray drying the slurry to prepare spray dried particles (e) [B], an interface A step [C] of preparing an activator composition (d), and a step [D] of adding and supporting the surfactant composition (d) on the spray-dried particles (e).

[Step [1]: Step [A]]
The slurry used in the step [A] may be a non-curable slurry that can be pumped, and such a slurry and each component constituting the slurry are as described above.
The temperature of a slurry becomes like this. Preferably it is 30-80 degreeC, More preferably, it is 35-65 degreeC. If it exists in this range, since the residual amount of water-soluble salts, such as sodium carbonate, decreases, it is preferable.
The slurry moisture is generally preferably 30 to 70% by mass, more preferably 35 to 60% by mass, and still more preferably 40 to 55% by mass. If the slurry moisture is within the above range, the amount of water-soluble salts dissolved is sufficient, and the increase in slurry viscosity can be suppressed, which is preferable in terms of pumping property. Moreover, since the amount of water evaporated in the step [B] is suppressed, productivity does not decrease.

  As a method for forming the slurry, the method and order of adding the components constituting the slurry can be appropriately changed depending on the situation. For example, all or almost all of the water is first added to the mixing vessel, preferably after the water temperature has nearly reached the set temperature, the other ingredients are added sequentially or simultaneously. As a normal order of addition, first, a water-soluble polymer or a liquid component such as a surfactant added as necessary is added, and then a water-soluble powder raw material such as a water-soluble salt is added. At this time, a small amount of auxiliary components such as a dye may be added. Next, a water-insoluble inorganic substance such as zeolite is added. For the purpose of improving the mixing efficiency, the water-insoluble inorganic substance may be added in two or more portions. In addition, powder raw materials such as water-insoluble inorganic substances and water-soluble salts may be mixed in advance and then added to an aqueous medium, or water may be added to adjust viscosity and slurry moisture after all components are added. . In order to finally obtain a homogeneous slurry, after all the components are added to the slurry, it is preferably mixed for 10 minutes or more, more preferably 30 minutes or more.

[Step [1]: Step [B]]
Step [B] is a step in which the slurry obtained in step [A] is spray-dried to prepare spray-dried particles (e). As a method for drying the slurry, spray drying in which the particle shape is substantially spherical is used. As the spray-drying tower, a countercurrent tower is more preferable because thermal efficiency and particle strength of the spray-dried particles are improved. The slurry atomizer may be any of a pressure spray nozzle, a two-fluid spray nozzle, and a rotating disk type, but a pressure spray nozzle is particularly preferable in order to obtain a desired average particle size.
The moisture of the spray-dried particles can be adjusted by adjusting the temperature of the gas supplied to the spray-drying tower and the amount of gas blown. As the gas to be supplied, those generally used for a heat medium can be used, and air, nitrogen and the like are exemplified. The temperature of the gas supplied to the spray-drying tower is preferably as high as possible in terms of oil absorption capacity, but in consideration of productivity, ease of production and safety, preferably 200 to 360 ° C. Preferably it is 220-340 degreeC, Most preferably, it is 240-320 degreeC. The temperature of the gas discharged from the spray drying tower is preferably 80 to 130 ° C., more preferably 80 to 125 ° C., and particularly preferably 80 to 120 ° C. in terms of thermal efficiency of the spray drying tower. Further, the spray-dried particles after spray-drying may be further dried by an air flow dryer, a fluidized bed dryer, a rotary dryer, or the like.

[Step [1]: Step [C]]
Step [C] is a step of preparing the surfactant composition (d). The surfactant composition (d) is a composition of at least one surfactant appropriately selected from an anionic surfactant, a nonionic surfactant, a zwitterionic surfactant, and a cationic surfactant. . As a method for adjusting the surfactant composition (d), if the surfactant to be used is liquid in a practical temperature range (room temperature to about 40 ° C.), the surfactant is mixed with these surfactants. The agent composition (d) is obtained, and the mixing method is not limited.

On the other hand, when using a solid or pasty surfactant in a practical temperature range (room temperature to about 40 ° C.), these are previously low-viscosity, for example, a nonionic surfactant, a nonionic surfactant aqueous solution, or A surfactant solution mixture or aqueous solution can be prepared by dispersing or dissolving in water, and a surfactant acid precursor can be prepared in a surfactant having a low viscosity, a surfactant aqueous solution, or water. It can also be prepared by a method of neutralizing with an alkali agent (for example, an aqueous caustic soda solution or an aqueous caustic potash solution).
The surfactant composition (d) thus obtained can be added to the spray-dried particles (e) obtained in step [B] in the form of the mixed solution or aqueous solution. In this way, a surfactant that is solid or pasty in a practical temperature range (room temperature to about 40 ° C.) can be easily added to the spray-dried particles (e). It is advantageous for manufacturing.

  The mixing ratio of a surfactant having a low viscosity as described above, a surfactant aqueous solution or water and a surfactant in the form of a solid or paste in a practical temperature range (room temperature to about 40 ° C.) is obtained. Alternatively, it is preferable to be in a viscosity range in which the aqueous solution can be sprayed. For example, in the case of polyoxyethylene dodecyl ether and sodium dodecylbenzenesulfonate, the ratio of both is in the range of 1: 1.4 to 1.4: 1. The surfactant composition (d) that can be easily sprayed can be obtained by adjusting.

[Step [1]: Step [D]]
Step [D] is a step of adding and supporting the surfactant composition (d) obtained in step [C] to the spray-dried particles (e) obtained in step [B].
The amount of the surfactant composition (d) supported on the spray-dried particles (e) used in the present invention is 5 to 80 with respect to 100 parts by mass of the spray-dried particles (e) from the viewpoint of exerting detergency. Mass parts are preferred, 5-60 parts by mass are more preferred, 10-60 parts by mass are more preferred, and 20-60 parts by mass are particularly preferred. Here, the amount of the surfactant composition (d) supported is the addition of the surfactant when a surfactant other than the surfactant composition (d) is added during the slurry preparation in the step [A]. It does not include the amount.

  Examples of the method for supporting the surfactant composition (d) on the spray-dried particles (e) include a method using a known mixer of batch type or continuous type. When the batch method is used, the mixing method is as follows. (1) The spray-dried particles (e) are charged into the mixer while the mixer is operated, and then the surfactant composition (d) is added. 2) Charge the spray-dried particles (e) and the surfactant composition (d) into the mixer little by little. (3) Charge a portion of the spray-dried particles (e) into the mixer and then the remaining spray-dried. A method such as charging the particles (e) and the surfactant composition (d) little by little can be employed. The surfactant composition (d) can also be added after the step [2] of adding a layered clay mineral described later. Among these methods, the above (1) is particularly preferable. Moreover, it is preferable to add surfactant composition (d) in a liquid state, and it is preferable to spray and add surfactant composition (d) in a liquid state.

As the mixer used in the step [D], a Henschel mixer (made by Mitsui Miike Chemical Co., Ltd.), a high speed mixer (made by Fukae Kogyo Co., Ltd.), a vertical granulator (manufactured by Powrec Co., Ltd.), Redige Preferred examples include a mixer (manufactured by Matsuzaka Giken Co., Ltd.), a pro-shear mixer (manufactured by Taiheiyo Kiko Co., Ltd.), a nauter mixer (manufactured by Hosokawa Micron Co., Ltd.), and the like. From the viewpoint of producing base detergent particles (a) containing a large amount of mononuclear detergent particles having excellent solubility, the spray-dried particles (e) are hardly subjected to a strong shearing force (the spray-dried particles are not easily disintegrated). In view of the dispersion efficiency of the surfactant composition (d), a device having good mixing efficiency is preferable. Among them, a horizontal mixing tank has a stirring shaft at the center of a cylinder, and a stirring blade is attached to this shaft to form a powder. A Readyge mixer, a Proshear mixer, etc., which are mixers (horizontal mixers) that perform mixing, are particularly preferred.
Alternatively, the surfactant composition (d) may be supported on the spray-dried particles (e) using the continuous apparatus of the above mixer. Examples of continuous mixers other than those described above include, for example, flexo-mix type (manufactured by POWREC Co., Ltd.), turbulizer (manufactured by Hosokawa Micron Co., Ltd.) and the like.

When a nonionic surfactant is used, a water-soluble nonionic organic compound having a melting point of 45 to 100 ° C. and a molecular weight of 1000 to 30000 (hereinafter, referred to as “melting point raising agent”) is used as necessary. The melting point raising agent), or this aqueous solution can be added before, simultaneously with, during or after the addition of the surfactant, or mixed in advance with the surfactant. By adding a melting point increasing agent, it is possible to suppress caking resistance and the ability of the surfactant in the detergent particle group to stain. Examples of the melting point raising agent used in the present invention include polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, pluronic type nonionic surfactant and the like.
The amount of the melting point increasing agent used is 5 parts by mass or less with respect to 100 parts by mass of the spray-dried particles (e) from the standpoint of maintaining the mononuclearity of the detergent particles, high-speed solubility, and suppression of stains and caking properties. Is preferably 3 parts by mass or less, most preferably not included. As a method for adding the melting point increasing agent, mixing with a surfactant in an arbitrary manner in advance or adding a melting point increasing agent after the addition of the surfactant may cause the detergent particles to stain and caking. It is advantageous for suppressing the above.

The temperature in the mixer is preferably higher than the melting point of the surfactant to be added in order to promote the loading of the surfactant composition (d). More specifically, the temperature is preferably higher than the melting point and up to 50 ° C higher than the melting point, more preferably 10 ° C to 30 ° C higher than the melting point. Moreover, when adding the acid precursor of the said surfactant at this process, it is more preferable if it heats up to the temperature which can react the acid precursor of the said anionic surfactant, and it mixes.
Moreover, the batch-type mixing time for obtaining suitable base detergent particles and the average residence time in continuous mixing are preferably 1 to 20 minutes, and more preferably 2 to 10 minutes.

Step [D] has a step of drying excess moisture while mixing and / or mixing with a mixer when an aqueous solution of the surfactant as described above is added in the preparation of the slurry. May be.
It is also possible to add a powder builder before the addition of the surfactant composition, simultaneously with the addition of the surfactant composition, during the addition of the surfactant composition, or after the addition of the surfactant composition. By adding a powder builder, the particle size of the base detergent particles can be controlled, and the cleaning power can be improved.

Here, the powder builder is a detergency enhancing agent for powders other than surfactants. Specifically, a base that exhibits sequestering ability such as zeolite and citrate, sodium carbonate (dense ash, light Ash), bases having alkaline ability such as potassium carbonate, bases having both sequestering ability and alkaline ability such as crystalline silicate, and other bases which increase ionic strength such as sodium sulfate. More specifically, for example, JP-A-5-279013, column 3, line 17 to column 6, line 24 (particularly, those fired and crystallized at 500 to 1000 ° C. are preferred). No. 7-89712, column 2, line 45 to column 9, line 34, JP-A-60-227895, page 2, lower right column, line 18 to page 4, upper right column, line 3 (particularly Table 2). The crystalline silicate described in (1) is preferable. Here, an alkali metal silicate having SiO ₂ / M ₂ O (where M represents an alkali metal) of 0.5 to 3.2, preferably 1.5 to 2.6 is preferably used.
As the usage-amount of the said powder builder, 1-80 mass parts is preferable with respect to 100 mass parts of spray-drying particles (e), 5-70 mass parts is more preferable, 10-60 mass parts is further more preferable. If the amount of the powder builder used is within this range, the mononuclearity of the detergent particles can be maintained, good high-speed solubility can be obtained, and the particle size can be controlled.

[Step [2]]
Step [2] is a step of adding the layered clay mineral (b) to the base detergent particles (a) obtained in step [1] to form an intermediate layer.
The addition method of the layered clay mineral (b) is not particularly limited, but the batch type or continuous type known mixer used in the step [D] is not easily subjected to a strong shearing force (base detergent). It is preferable that the layered clay mineral (b) is appropriately dispersed on the surface of the base detergent particles because the particles are difficult to disintegrate and the mixing efficiency is high (high dispersibility).
The batch mixing time and the average residence time in the continuous mixing are preferably 1 to 20 minutes and more preferably 2 to 20 minutes from the viewpoint of obtaining detergent particles having a preferable intermediate layer.

In the step [2], it is preferable to add a binder component because adhesion of the layered clay mineral (b) and the surface modifier (c) is increased. As a method for adding the binder component, (1) the layered clay mineral (b) is added to the base detergent particles (a) inside the mixer while the mixer is operated, and then the binder component is added ( 2) Add the binder component and then add the layered clay mineral (b). (3) Add the layered clay mineral (b) and the binder component simultaneously. (4) Add the layered clay mineral (b) and the binder component. It is possible to take a method such as adding little by little alternately.
Moreover, when using 2 or more types of binder components, you may add simultaneously and may add separately before and after adding a layered clay mineral (b) to a mixer. The binder component that is solid at room temperature is preferably supplied after being melted, and is preferably supplied by spraying at a temperature higher than the internal temperature of the mixer.

  It is also possible to add a powder builder simultaneously with or during the addition of the layered clay mineral (b). By adding a powder builder, the particle diameter of the detergent particles can be controlled, and the cleaning power can be improved. Here, as a powder builder, what was illustrated by process [D] is used preferably.

[Step [3]]
Step [3] is a step of surface-modifying the particles having the intermediate layer obtained in step [2] with a surface modifier (c), and the step of adding the surface modifier (c) described above At least one step is performed. By passing the step [3] of adding the surface modifier (c) to the particles having an intermediate layer formed of the layered clay mineral (b) on the surface of the base detergent particles (a), High-speed solubility, fluidity and non-caking properties can be improved.
The apparatus used in the step [3] is not particularly limited, and a known mixer can be used, but the mixer exemplified in the above step [D] is preferably used. The mixing time using the mixer is preferably 0.1 to 5 minutes, more preferably 0.5 to 3 minutes, from the viewpoint of sufficiently adding the surface modifier (c) onto the intermediate layer. The mixing process by a mixer is performed at least once.

The detergent particles thus obtained are preferably a mononuclear detergent particle group having the base cleaning particles (a) as a core. The mononuclear detergent particles are cleaning particles in which the base detergent particles (a) are loaded with the layered clay mineral (b), the surface modifier (c), and other components added as necessary. That is, it refers to a detergent particle having one base detergent particle (a) as a core in one detergent particle. A method for producing such a mononuclear detergent particle group is sometimes referred to as a mononuclear granulation method. As a factor showing this mononuclearity, the degree of particle growth can be used, and the degree of particle growth of the detergent particles obtained in the step [3] is expressed by the following formula:
Particle growth degree = (average particle diameter of detergent particles) / (average particle diameter of base detergent particles (a))
It is represented by The particle growth degree of the detergent particle group obtained in the step [3] is preferably 1.5 or less, more preferably 1.3 or less, and further preferably 1.2 or less from the viewpoint of the dissolution rate in washing. In such a detergent particle group, aggregation between particles is suppressed, so that generation of aggregated particles, for example, outside the range of the average particle diameter of the desired detergent particles is suppressed, and the amount of surfactant added The variation in the average particle size and particle size distribution of the detergent particles obtained with respect to the variation in the number of particles is reduced, so that uniform detergent particles can be obtained in a high yield.

[Detergent composition]
The detergent composition of the present invention is a composition containing the cleaning particles obtained in the step [3], and is obtained, for example, by mixing the detergent particles and a separately added detergent component. The detergent composition of the present invention can be used without particular limitation as long as it is an application using a powder detergent. For example, it can be preferably used as a powder detergent for clothing, a detergent for automatic dishwashers and the like.
As detergent components added separately, for example, known detergent base materials such as surfactants and builder granules, bleaching agents (percarbonate, perborate, bleach activator, etc.), bleach activators, Examples thereof include anti-staining agents (such as carboxymethyl cellulose), softening agents, reducing agents (such as sulfites), fluorescent brighteners, antifoaming agents (such as silicone), enzymes such as cellulase and protease, dyes, and fragrances.
The content of the detergent particles in the detergent composition is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more from the viewpoint of detergency. The content of the separately added detergent component in the detergent composition is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less. .

The detergent composition produced by the production method of the present invention was evaluated according to the following method.
1. The average particle diameter was determined using a sieve specified in JIS Z 8801.
For example, using a 9-stage sieve and a saucer having openings of 2000 μm, 1400 μm, 1000 μm, 710 μm, 500 μm, 355 μm, 250 μm, 180 μm and 125 μm, a low-tapping machine (made by HEIKO SEISAKUSHO, tapping: 156 times / min, rolling: 290 times / minute), 100 g of the sample was shaken for 5 minutes and sieved, and then the saucer and each sieve in the order of 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, 2000 μm. When the mass frequency is accumulated below, the opening of the first sieve with an accumulated mass frequency of 50% or more is x _j μm, and the opening of the sieve smaller by one is x _{j + 1} μm. When the sum of the mass frequency from the saucer to the x _j μm sieve is Q _j %, x from the saucer _When the sum of the mass frequency up to the _{j + 1} μm sieve is Q _{j + 1} %, it can be obtained by the following equation. The average particle size x _a can be obtained by the formulas (1) and (2).

2. Bulk density It measured by the method prescribed | regulated by JISK3362.
3. Moisture Measured by a method defined by JIS K0068.
4). Storage stability (screening rate)
Using a filter paper (No. 2 manufactured by ADVANTEC), make a box without a top with a length of 10.2 cm, a width of 6.2 cm, and a height of 4 cm, and fix the four corners with a stapler. Into this, 50 g of the detergent composition obtained in each example and comparative example is put, and an acrylic resin plate (15 g) and a lead plate (250 g) are placed on the box. This is a temperature 30 ° C., a humidity 70% R.D. H. The passing rate specified in the following was determined for the caking state after being left for 21 days and 28 days in an atmosphere.
Sieve passing rate: The sample after the test is gently opened on a sieve (aperture 4760 μm defined in JIS Z 8801), the weight of the passed powder is measured, and the sieve passing rate (%) with respect to the sample after the test is obtained.
5. Resistance to caking (stain out)
The state of spotting at the bottom (non-contact surface with the powder) of the filter paper container subjected to the sieve passing rate test was visually observed and evaluated according to the following criteria of 1 to 5 ranks.
Rank 1: not wet.
Rank 2: The surface of about 1/4 is wet.
Rank 3: about 1/2 surface is wet.
Rank 4: The surface of about 3/4 is wet.
Rank 5: The entire surface is wet.

In the examples, the following raw materials are used unless otherwise specified.
Sodium sulfate: manufactured by Shikoku Kasei Co., Ltd., product name: anhydrous neutral sodium sulfate, sodium sulfite: manufactured by Mitsui Chemicals, Inc., product name: sodium sulfite, fluorescent dye: manufactured by Ciba Specialty Chemicals, Inc., product name: Chino Pearl CBS-X
Sodium carbonate: manufactured by Central Glass Co., Ltd., product name: dense ash, average particle size: 290 μm
Sodium polyacrylate aqueous solution: manufactured by Kao Corporation, weight average molecular weight: 10,000 Crystalline aluminosilicate: manufactured by Zeobuilder, 4A type, average particle size: 3.5 μm
Sodium dodecylbenzenesulfonate: manufactured by Kao Corporation, product name: Neoperex G-25, solid content: 26% by mass
Soap: manufactured by Kao Corporation, product name: NS soap, solid content: 90%
Polyethylene glycol: manufactured by Mitsui Chemicals, Inc., product name: PEG 13000, weight average molecular weight: 10,000, solid content: 60%
Polyoxyethylene alkyl ether (nonionic surfactant): manufactured by Kao Corporation, product name: Emulgen 108KM (average number of moles of ethylene oxide added: 8.5, carbon number of alkyl chain: 12-14)
Dodecylbenzenesulfonic acid: 38% by mass of Lunac L-98 (manufactured by Kao Corporation), 12% by mass of Lunac MY-98 (manufactured by Kao Corporation), and 50 of Lunac P-95 (manufactured by Kao Corporation) It was obtained by blending at a mass percentage.
Crystalline sodium silicate: manufactured by Tokuyama Siltech Co., Ltd., product name: Prefeed 6N with an average particle size of 10 μm

Preparation Example 1: Preparation of spray-dried particles 1 410 parts by mass of water was added to a 1 m ³ mixing tank having a stirring blade, and after the water temperature reached 45 ° C., 110 parts by mass of sodium sulfate, 8 parts by mass of sodium sulfite, fluorescence 2 parts by weight of the dye was added and stirred for 10 minutes. Next, 120 parts by weight of sodium carbonate and 150 parts by weight of a 40% by weight aqueous sodium polyacrylate solution were added and stirred for 10 minutes, and further 40 parts by weight of sodium chloride and 160 parts by weight of crystalline aluminosilicate were added for 15 minutes. By stirring, a homogeneous slurry having a slurry water content of 50% by mass was obtained. The final temperature of this slurry was 50 ° C.
While supplying nitrogen gas at 285 ° C from the bottom of the tower to the spray drying tower, the slurry is supplied to the spray drying tower (counterflow type) by a pump and sprayed at a spray pressure of 2.5 MPa from a pressure spray nozzle installed near the top of the tower. Went. Nitrogen gas was discharged at 98 ° C. from the top of the column. The obtained spray-dried particles 1 had a water content of 0%, an average particle size of 290 μm, a bulk density of 510 g / L, a supporting capacity of 65 mL / 100 g, and a particle strength of 350 kg / cm ² .

Preparation Example 2: Preparation of spray-dried particles 2 15 parts by weight of water and 808 parts by weight of sodium dodecylbenzenesulfonate are added to a 1 m ³ mixing tank having a stirring blade, and after the water temperature reaches 45 ° C., 33 parts by weight of soap. 60 parts by weight of polyoxyethylene alkyl ether, 125 parts by weight of 40% by weight sodium polyacrylate aqueous solution, and 22 parts by weight of polyethylene glycol were added and stirred for 5 minutes. Next, 45 parts by weight of sodium sulfate, 10 parts by weight of sodium sulfite, and 2 parts by weight of fluorescent dye were added and stirred for 5 minutes, 140 parts by weight of sodium carbonate was further added, and 140 parts by weight of crystalline aluminosilicate was added, The mixture was stirred for 15 minutes to obtain a homogeneous slurry having a slurry water content of 50% by mass. The final temperature of this slurry was 50 ° C.
While supplying nitrogen gas at 200 ° C from the bottom of the tower to the spray drying tower, the slurry is supplied to the spray drying tower (counterflow type) by a pump and sprayed at a spray pressure of 2.5 MPa from a pressure spray nozzle installed near the top of the tower. Went. Nitrogen gas was discharged at 98 ° C. from the top of the column. The obtained spray-dried particles 1 had a water content of 0%, an average particle size of 290 μm, a bulk density of 510 g / L, a supporting capacity of 10 mL / 100 g, and a particle strength of 120 kg / cm ² .

Preparation Example 3: Preparation of Surfactant Composition 840 parts by mass of polyoxyethylene alkyl ether and 69 parts by mass of polyethylene glycol were heated to 80 ° C., 960 parts by mass of dodecylbenzenesulfonic acid, and 258 parts by mass of 48% aqueous sodium hydroxide solution. Was added and stirred to prepare a surfactant composition containing 10.3% by mass of water.

Example 1: Preparation of detergent particle 1 50 parts by weight of spray-dried particles 1 and 9.3 parts by weight of sodium carbonate were put into a Redige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity 130 L, with jacket). Stirring at a rotating speed of the stirring blade: 60 rpm, peripheral speed: 1.6 m / s) was started. Warm water at 80 ° C. was passed through the jacket at 10 L / min. Thereto, 21.3 parts by mass of the surfactant composition obtained in Preparation Example 3 heated to 80 ° C. (effective portion 19.1 parts by mass, moisture 2.2 parts by mass) was charged over 2 minutes, Thereafter, stirring was performed for 5 minutes, and the surfactant composition was supported on the spray-dried particles 1 to obtain base detergent particles 1.
Next, 0.92 parts by mass of fatty acid heated to 80 ° C. was added while spraying, and then stirred for 5 minutes. Thereby, this fatty acid reacts with 0.2 mass part sodium carbonate, and becomes 1 mass part soap. 1.7 parts by weight of polyethylene glycol (effective part 60% by weight) (effective part 1.0 part by weight, moisture 0.7 part by weight) is added, and layered clay mineral (manufactured by Zude Chemi, product name: Round Rosil DGA powder) 1 part by mass and 2 parts by mass of crystalline sodium silicate were added and stirred for 5 minutes. Next, 5 parts by mass of crystalline aluminosilicate was added, and stirring of the main shaft (rotation speed: 120 rpm, peripheral speed: 3.1 m / s) and chopper (rotation speed: 3600 rpm, peripheral speed: 28 m / s) was performed. For a second. The operating conditions of the Redige mixer are returned to the main shaft (stirring blade, rotation speed: 60 rpm, peripheral speed: 1.6 m / s), and 10 parts by mass of crystalline aluminosilicate is added. Further, the main shaft (rotation speed: 120 rpm, peripheral speed: 3.1 m / s) and chopper (rotation speed: 3600 rpm, peripheral speed: 28 m / s) were stirred for 30 seconds, then discharged, and the detergent of Example 1 Particle 1 was obtained. By the time of discharge, 38% of the water contained in the surfactant composition and polyethylene glycol was evaporated, and the water content in the detergent particles 1 was 1.8 parts by mass. The composition and evaluation of the resulting detergent particles 1 are shown in Table 1.

Examples 2 to 7 and Comparative Example 1: Preparation of detergent particles 2 to 7 and detergent particles A. Except that the spray-dried particles, sodium carbonate, and layered clay mineral used were the conditions shown in Table 1. In the same manner as in Example 1, detergent particles 2 to 7 were obtained. The composition and evaluation of the obtained detergent particles 2 to 7 are shown in Table 1.

Example 8: Preparation of detergent particles 8 First, a layered clay mineral (manufactured by Zoot Chemi, product name: Round Rosil DGA212, average particle size: 720 μm) was averaged using a hammer mill type grinder, and the average particle size was 18 μm, 45 μm. , And 68 μm of three types of layered clay minerals were prepared.
50 parts by mass of spray-dried particles 1, 5.5 parts by mass of sodium carbonate, and 2 parts by mass of crystalline sodium silicate were put into a Redige mixer (Matsuzaka Giken Co., Ltd., capacity 130 L, with jacket), Stirring was started (rotation speed of stirring blade: 60 rpm, peripheral speed: 1.6 m / s). Warm water at 80 ° C. was passed through the jacket at 10 L / min. Thereto, 21.3 parts by mass of the surfactant composition obtained in Preparation Example 3 heated to 80 ° C. (effective portion 19.1 parts by mass, moisture 2.2 parts by mass) was charged over 2 minutes, Thereafter, stirring was performed for 5 minutes, and the surfactant composition was supported on the spray-dried particles 1 to obtain base detergent particles 1.
7 parts by mass of layered clay mineral (manufactured by Zude Chemi, product name: round rosyl DGA212 crushed to an average particle size of 18 μm) was added thereto, followed by stirring for 5 minutes. Next, 5 parts by mass of crystalline aluminosilicate was added, and stirring of the main shaft (rotation speed: 120 rpm, peripheral speed: 3.1 m / s) and chopper (rotation speed: 3600 rpm, peripheral speed: 28 m / s) was stirred for 30 seconds. went. The operating condition of the Redige mixer is returned to the main shaft (stirring blade, rotation speed: 60 rpm, peripheral speed: 1.6 m / s), and 10 parts by mass of crystalline aluminosilicate is added. Further, the main shaft (rotation speed: 120 rpm, peripheral speed: 3.1 m / s) and chopper (rotation speed: 3600 rpm, peripheral speed: 28 m / s) were stirred for 30 seconds, then discharged, and the detergent of Example 8 Particles 8 were obtained. By the time of discharge, 38% of the moisture contained in the surfactant composition and polyethylene glycol was evaporated, and the moisture in the detergent particles 8 became 1.4 parts by mass. The composition and evaluation of the resulting detergent particles 8 are shown in Table 1.

Examples 9 to 10: Preparation of detergent particles 9 to 10 Round rosyl DGA212 (product name, manufactured by Zoot Chemi) having an average particle diameter of 18 μm used as the layered clay mineral in Example 8 has an average particle diameter of 45 μm and 68 μm, respectively. Detergent particles 9 and 10 were obtained in the same manner as in Example 8 except that the product was changed to a different one. The composition and evaluation of the resulting detergent particles 9 and 10 are shown in Table 1.

Comparative Example 2: Preparation of detergent particles B Except that round rosyl DGA212 (product name, manufactured by Zoot Chemi Co., Ltd.) having an average particle diameter of 18 μm used as a layered clay mineral in Example 8 was changed to an unmilled average particle diameter of 720 μm. In the same manner as in Example 8, detergent particles B were obtained. Table 1 shows the composition and evaluation of the obtained detergent particles B.

Example 11: Preparation of detergent particles 11 Detergent particles 11 were obtained in the same manner as in Example 8, except that the layered clay mineral of Example 8 was EXM0242 (product name, manufactured by Zoot Chemi). The composition and evaluation of the resulting detergent particles 11 are shown in Table 1.

Example 12: Preparation of detergent particles 12 A Readyge mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity 130 L, with jacket) was charged with 40 parts by mass of sodium carbonate and 15 parts by mass of crystalline sodium silicate, and the main shaft (stirring) Agitation was started at a blade rotation speed of 60 rpm and a peripheral speed of 1.6 m / s. Warm water at 80 ° C. was passed through the jacket at 10 L / min. Thereto, 10 parts by mass of polyoxyethylene alkyl ether was added over 1 minute, and then stirred for 5 minutes to obtain base detergent particles 12.
15 parts by mass of layered clay mineral (manufactured by Sud Kemi Co., Ltd., product name: round rosyl DGA powder) was added thereto and stirred for 5 minutes. Next, 20 parts by mass of crystalline aluminosilicate was added, and stirring of the main shaft (rotation speed: 120 rpm, peripheral speed: 3.1 m / s) and chopper (rotation speed: 3600 rpm, peripheral speed: 28 m / s) was performed for 30 seconds. After performing, it discharged | emitted and the detergent particle | grains 12 of Example 12 were obtained. The composition and evaluation of the obtained detergent particles 12 are shown in Table 1.

Comparative Example 3: Preparation of detergent particles C Detergent particles C were obtained in the same manner as in Example 12 except that the amount of sodium carbonate used in Example 12 was 45 parts by mass and no layered clay mineral was added. The composition and evaluation of the obtained detergent particles C are shown in Table 1.

Example 13: Preparation of detergent particles 13 In a Redige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity 130 L, with jacket), 70 parts by mass of spray-dried particles 2, 3 parts by weight of sodium carbonate, and crystalline sodium silicate 2 A mass part was charged, and stirring of the main shaft (rotation speed of stirring blade: 60 rpm, peripheral speed: 1.6 m / s) was started. Warm water at 80 ° C. was passed through the jacket at 10 L / min. Thereto, 3 parts by mass of polyoxyethylene alkyl ether was added over 1 minute, and then stirred for 5 minutes to obtain base detergent particles 13 in which the spray-dried particles 2 carry the surfactant composition.
7 parts by mass of layered clay mineral (manufactured by Sud Kemi Co., Ltd., product name: round rosyl DGA powder) was added thereto and stirred for 5 minutes. Next, 5 parts by mass of crystalline aluminosilicate was added, and stirring of the main shaft (rotation speed: 120 rpm, peripheral speed: 3.1 m / s) and chopper (rotation speed: 3600 rpm, peripheral speed: 28 m / s) was stirred for 30 seconds. went. The operating condition of the Redige mixer is returned to the main shaft (stirring blade, rotation speed: 60 rpm, peripheral speed: 1.6 m / s), and 10 parts by mass of crystalline aluminosilicate is added. Further, the main shaft (rotation speed: 120 rpm, peripheral speed: 3.1 m / s) and chopper (rotation speed: 3600 rpm, peripheral speed: 28 m / s) were stirred for 30 seconds, then discharged, and the detergent of Example 13 Particles 13 were obtained. The composition and evaluation of the obtained detergent particles 13 are shown in Table 1.

Example 14: Preparation of detergent particles 14 In a Redige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity 130 L, with jacket), 50 parts by mass of spray-dried particles 1, 5.5 parts by mass of sodium carbonate, and crystalline silicic acid 2 parts by mass of sodium was added, and stirring of the main shaft (rotation speed of stirring blade: 60 rpm, peripheral speed: 1.6 m / s) was performed for 5 minutes. Warm water at 80 ° C. was passed through the jacket at 10 L / min. 7 mass parts of layered clay mineral (product name: Round Rozil DGA212, crushed to an average particle size of 18 μm) was added thereto, stirred for 5 minutes, and then heated to 80 ° C. 21.3 parts by mass of the surfactant composition obtained in Example 3 (effective amount 19.1 parts by mass, moisture 2.2 parts by mass) was added over 2 minutes, and then stirred for 5 minutes.
Next, 5 parts by mass of crystalline aluminosilicate was added, and stirring of the main shaft (rotation speed: 120 rpm, peripheral speed: 3.1 m / s) and chopper (rotation speed: 3600 rpm, peripheral speed: 28 m / s) was stirred for 30 seconds. went. The operating condition of the Redige mixer is returned to the main shaft (stirring blade, rotation speed: 60 rpm, peripheral speed: 1.6 m / s), and 10 parts by mass of crystalline aluminosilicate is added. Further, the main shaft (rotation speed: 120 rpm, peripheral speed: 3.1 m / s) and chopper (rotation speed: 3600 rpm, peripheral speed: 28 m / s) were stirred for 30 seconds, then discharged, and the detergent of Example 14 Particles 14 were obtained. By the time of discharge, 38% of the moisture contained in the surfactant composition and polyethylene glycol was evaporated, and the moisture in the detergent particles 14 was 1.4 parts by mass. The composition and evaluation of the obtained detergent particles 14 are shown in Table 1.

In each of Examples 1 to 7, the layered clay mineral is blended within the range in which the effect of the present invention can be expected, and an intermediate layer of the layered clay mineral is formed. Accordingly, the blended amount of the layered clay mineral is less than the range of the present invention, and the storage stability is excellent in terms of both the sieve passing rate and the stain bleeding property as compared with Comparative Example 1 in which the formation of the intermediate layer cannot be expected.
As a balance component for increasing the amount of layered clay mineral, the effect of the present invention is exhibited even when the spray-dried particles are reduced or the sodium carbonate particles are reduced, but the effect is reduced when the sodium carbonate particles are reduced. Is big.

  About Examples 8-10, it is mix | blended after crushing the granulated layered clay mineral so that it may become the average particle diameter in the range of this invention. Therefore, compared with Comparative Example 2 in which the layered clay mineral granule having an average particle size larger than the range of the present invention is blended, the storage stability is excellent in terms of both the sieve passing rate and the bleediness. Examples 8 to 10 all exhibit the effects of the present invention, but the smaller the average particle size, the greater the effect of improving storage stability.

For Example 11, a layered clay mineral with a higher calcium content than that used in Examples 1-10 is used. Although the effect is less than that of Examples 1 to 10, the effect of forming an intermediate layer by the layered clay mineral of the present invention is also exhibited in Example 11.
Even in the case of base detergent particles having a very simple composition that does not use spray-dried particles as in Example 12, the effect of forming an intermediate layer with the layered clay mineral of the present invention is exhibited, and the storage stability is superior to Comparative Example 3. .
As in Example 14, it was shown that even when the layered clay mineral was added before the addition of the surfactant composition, the effect of forming the intermediate layer formed by the layered clay mineral was exhibited.
Moreover, the detergent particles 1-14 which are the Example of this invention have the bulk density suitable for a compact detergent, and have the average particle diameter which can anticipate sufficient solubility as a detergent.

  1 and 2 are SEM photographs of a cross-section of the detergent particles obtained in Example 1 of the present invention. In the detergent particle | grains of this invention, it turns out that the intermediate | middle layer comprised with a layered clay mineral (b) is formed with the fixed thickness on the surface of base detergent particle | grains (a). Moreover, in the case of the detergent particle obtained in Example 1, it turns out that the surface modifier (c) is taken in in the intermediate | middle layer which a layered clay mineral (b) makes.

It is a SEM photograph of the section of detergent particles of the present invention. It is a SEM photograph of the section of detergent particles of the present invention.

Claims (10)

1 to 25 parts by mass of layered clay mineral (b) having an average particle diameter of 7 μm or more and 60 μm or less and an average particle diameter of primary particles of 0.1 to 10 μm with respect to 100 parts by mass of the base detergent particles (a).
An intermediate layer containing the layered clay mineral (b) is formed on the surface of the base detergent particles (a), and the surface modification is performed on the intermediate layer. Detergent particles to which agent (c) is added. The layered clay mineral (b) has the following general formula (I):
_{[Si 8 (Mg a Al b} ) O 20 (OH) 4] X- · Me X + (I)
(Wherein a, b and x are 0 <a ≦ 6, 0 <b ≦ 4, x = 12-2a-3b, M
e is at least one ion selected from Na, K, Li, Ca _1/2 , Mg _1/2 and NH ₄ . Moreover, the molar ratio (Na + K + Li) / (Ca + Mg) of the alkali metal ion and the alkaline earth metal ion represented by the following formula among the ions is 1.0 or more. )
The detergent particle | grains of Claim 1 represented by these. The detergent particles according to claim 1 or 2, wherein the base detergent particles (a) are obtained by supporting a surfactant composition (d) on spray-dried particles (e) that do not contain a surfactant. For 100 parts by mass of the base detergent particles (a), the binder component is further 0.5 to
The detergent particle according to any one of claims 1 to 3, obtained by adding 8 parts by mass. Obtained in the step [1] for preparing the base detergent particles (a), the step [2] for adding the layered clay mineral (b) to the base detergent particles (a) to form an intermediate layer, and the step [2]. The detergent particle according to any one of claims 1 to 3, obtained by undergoing a step [3] of surface-modifying particles having an intermediate layer with a surface modifier (c). Step (A) in which the base detergent particles (a) prepare a slurry, Step (B) in which the slurry is spray-dried to prepare spray-dried particles (e), and a surfactant composition (d) is prepared. It is prepared by the step [C] and the step [1] having the step [D] of adding and supporting the surfactant composition (d) to the spray-dried particles (e). The detergent particle according to any one of 5. In the step [2], the base detergent particles (a)
(1) A method of adding a binder component after adding the layered clay mineral (b),
(2) A method of adding a layered clay mineral (b) after adding a binder component,
(3) A method of simultaneously adding the layered clay mineral (b) and the binder component, and (4) a method of alternately adding the layered clay mineral (b) and the binder component little by little,
The detergent particle according to claim 5, which is performed by a method selected from: In the step [3], the surface modifier (c) is added to the particles having the intermediate layer obtained in the step [2].
The detergent particle according to claim 5, wherein the detergent particle is a step of performing at least one step of adding the detergent. The detergent particle according to any one of claims 1 to 8, wherein the surface modifier (c) is crystalline or amorphous aluminosilicate.   A detergent composition containing the detergent particles according to claim 1.

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